CN101759914A - Mineral/whisker toughening-reinforcing polypropylene composition - Google Patents
Mineral/whisker toughening-reinforcing polypropylene composition Download PDFInfo
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- CN101759914A CN101759914A CN200810203130A CN200810203130A CN101759914A CN 101759914 A CN101759914 A CN 101759914A CN 200810203130 A CN200810203130 A CN 200810203130A CN 200810203130 A CN200810203130 A CN 200810203130A CN 101759914 A CN101759914 A CN 101759914A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a mineral/whisker toughening-reinforcing polypropylene composition, which is prepared from the following raw materials in percentage by weight: 50 to 70 percent of polypropylene, 3 to 15 percent of whisker reinforcing agent, 15 to 35 percent of other inorganic filler, 3 to 10 percent of PP compatilizer, 0.1 to 2 percent of antioxidant and 0 to 5 percent of other additives. The composition adopts polypropylene as matrix resin, solves the problems of low rigidity, poor strength, not high heat resistance and the like of polypropylene serving as a raw material of engineering components by adopting a mineral/whisker composite toughening-reinforcing technique, greatly improves the impact strength of material through the composite toughening-reinforcing technique, and expands the application fields of the polypropylene serving as engineering components. Meanwhile, mineral/whisker composite reinforcement solves the problem of size instability of polypropylene products.
Description
Technical field
The present invention relates to a kind of mineral/whisker reinforced polypropylene composition, can be used for automobile-used product, household electrical appliances product etc., belong to the polypropylene technology field.
Background technology
Polypropylene is as a kind of general-purpose plastics, it has characteristics such as processing characteristics is good, good mechanical property, chemical resistance, in plastics, occupy critical role, but when making engineering part, its intensity, rigidity and thermotolerance far can not meet the demands, and the polypropylene impact property is poor simultaneously, particularly low temperature impact properties is poor, molding shrinkage is big, and particularly aspect ratio is shunk shortcomings such as inhomogeneous during fiber reinforcement, and this has limited the application of polypropylene in engineering part.
Utilize the Inorganic Fillers Filled polypropylene to obtain the modified polypropylene material of low-cost and high-performance, be one of effective, the most most economical approach that obtains in the high performance polymer matrix material, especially obtained good effect aspect the intensity of material, rigidity, heat-drawn wire and the dimensional stability improving.Over surplus in the of nearest ten year, the toughness reinforcing theory of inorganic rigid particle, expressing technique theory and practice, inorganic modified dose of process for treating surface fast development, changed in the past with inorganic material-modified must be to sacrifice the situation that some performance index is a cost.
Whisker is the fiber that a kind of monocrystalline form growth forms, and diameter is minimum, has the atomic arrangement of high-sequential, does not have big lattice defect, has had high intensity and modulus, can give matrix material high intensity.Compare with glass, the easier and resin compounded of whisker, the material isotropy, visual appearance is good, is fit to very much make the product complex-shaped, that dimensional precision is high, surface smoothness is high.But the whisker modified polypropylene composite material that obtains of simple at present use, it is so obvious that toughening effect can not show a candle to reinforced effects, and the matrix material erosion-resisting characteristics of gained still requires to have certain distance with reality.
Use the rubber-like elastomerics can tenacity-increased profax, yet this method be often brought the significantly consequence that declines to a great extent of raising and intensity, rigidity, modulus and thermotolerance of material cost.The further investigation of inorganic rigid particle toughening polyolefine, inorganic rigid particle toughening polyolefine material has dropped in the practical application, therefore the present invention uses for reference the toughness reinforcing theory of inorganic rigid particle, use special coupling system and complete processing, it is higher to obtain intensity and toughness, and performance is the equilibrated modified polypropylene material more.
Chinese patent CN 1532221A discloses a kind of way for preparing mineral/whisker reinforced polypropylene composition, this method strengthens toughness reinforcing effect by composite the reaching of mineral toughener, magnesium salt whisker and plasticizing mother particle, yet because the limitation of working method and selection, effect is not particularly good; Chinese patent CN 101020775A has introduced a kind of high strength and high toughness modified poly-propylene material preparation, it mainly is to reach toughness reinforcing effect by mineral enhancing and beta nucleater and elastomerics, the cost of this method is higher, and intensity and toughness improve comparatively limited; The cost of matrix material is than higher, and mechanical property can also further improve; Chinese patent CN 1468897A has introduced the preparation method of the polypropylene composite material of a kind of potassium titanate crystal whisker and glass fibre, prepared product strength and toughness are all than higher, yet the use of glass can influence the outward appearance of product, and being easy to generate warpage etc., this has just limited the use range of this material; Chinese patent CN 1406792A has introduced a kind of preparation method who uses calcium sulfate crystal whiskers to strengthen the bumper special material of filling, and use elastomericss such as POE among this preparation method in a large number, so cost is higher; In addition, Chinese patent CN1011139734A and CN 101092734A disclose some novel calcium salt Preparation of Whiskers methods, and at superpolymer, particularly the application in polypropylene does not all relate to it.
Summary of the invention
The purpose of this invention is to provide a kind of mineral/whisker toughening-reinforcing polypropylene composition with high-impact, high rigidity and low-shrinkage, low warpage.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of composition of mineral/whisker toughening-reinforcing polypropylene, formulated by following raw materials by weight percent:
Polypropylene 50-70
Whisker toughener 3-15
Other mineral fillers 15-35
PP compatilizer 3-10
Oxidation inhibitor 0.1-2
Other auxiliary agents 0-5
Described polypropylene is different mobile homo-polypropylene and block copolymerization propylene.Wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4～10mol%, the degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%, polyacrylic melt flow rate (MFR) (test condition: 230 ℃ * 2.16kg) be 2～60g/10min.
Described whisker toughener is the calcium salt whisker, its length-to-diameter ratio L/D＞40, particle diameter＜10 μ m.Described other mineral fillers are talcum powder, lime carbonate, mica, barium sulfate or their composition, and its particle size range is 1～10 micron.
Described PP compatilizer is the oligopolymer of the graftomer of polypropylene and maleic anhydride, and its melt flow rate (MFR) is 5-30g/10min, and the maleic anhydride graft amount is 0.5-2.5%.
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select for use hindered phenol or thioesters kind antioxidant as 3114,1010, DSTP wherein one or more; Auxiliary anti-oxidant can select for use the phosphorite kind antioxidant as 618,168 etc.
Described other additives comprise one or more of shades of colour additive, photostabilizer, various ester class or fatty acid lubricant etc.
Preparation method of the present invention is as follows:
(1) takes by weighing raw material by proportioning;
(2) with mineral surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(3) with calcium salt whisker surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(4) place high mixer together under 90-120 ℃ of condition polypropylene, other mineral fillers, PP grafting compatilizer, oxidation inhibitor and other auxiliary agent, mixed 3 minutes;
(5) raw materials mixed is placed dual-screw-stem machine,, the calcium salt whisker is joined in the forcing machine by the way of side direction feeding, extruding pelletization, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
The present invention adopts polypropylene as matrix resin, by adopting mineral/whisker composite toughening enhancement techniques, both solved that polypropylene is low as the rigidity of engineering part raw material, intensity difference, thermotolerance not high defective, simultaneously by this composite toughening enhancement techniques, the shock strength of material is improved greatly, enlarged the Application Areas of polypropylene, simultaneously as the engineering product, the compound enhancing of mineral/whisker has solved the unsettled defective of polypropylene articles size.
Advantage of the present invention is that mineral/whisker reinforced polypropylene has high strength, high rigidity, and shock resistance, fire-retardant, dimensional stabilizing are suitable for all kinds of automobile-used, household electrical appliances engineering plastics spares of injection molding.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, polypropylene is that melt flow rate (MFR) is 2～60g/10min (test condition: 230 ℃ * 2.16kg) homo-polypropylene and block copolymerization propylene, wherein the comonomer of block copolymerization propylene is common is ethene, and its content is in the scope of 4～10mol%; The degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.The whisker toughener is the calcium salt whisker, its length-to-diameter ratio L/D＞40, particle diameter＜10 μ m.Described other mineral fillers are talcum powder, and its particle size range is 10 microns.Toughner POE is linear ethylene-octene copolymer that E.I.Du Pont Company produces, and density is 0.86～0.90g/cm
3, melting index is 0.5～20g/10min (test condition: 190 ℃ * 2.16kg).The PP compatilizer is the oligopolymer of the graftomer of polypropylene and maleic anhydride, and its melt flow rate (MFR) is 5-30g/10min, and the maleic anhydride graft amount is 0.5-2.5%.Primary antioxidant is the DSTP that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester, and Ciba company produce 3114, trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of Ciba company product, and trade names are Irgafos 168, and chemical name is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Described photostabilizer is 944 of Ciba company product, and chemical name is poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] }, and Ciba company produce 770, chemical name be pairs (2,2,6, the 6-tetramethyl-piperidyl) sebate.Comprise shades of colour additive, various ester class or fatty acid lubricant etc. in addition.
The preparation method is as follows:
(1) takes by weighing raw material by proportioning;
(2) with mineral surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(3) with calcium salt whisker surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(4) place high mixer together under 90-120 ℃ of condition polypropylene, other mineral fillers, PP grafting compatilizer, oxidation inhibitor and other auxiliary agent, mixed 3 minutes;
(5) raw materials mixed is placed dual-screw-stem machine,, the calcium salt whisker is joined in the forcing machine by the way of side direction feeding, extruding pelletization, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 90～100 ℃ convection oven dry 2～3 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.
The tensile property test is undertaken by ISO 527-2, and specimen size is 170*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*10*4mm, and notch depth is 1/3rd of a sample thickness.
Comprehensive mechanical performance is passed judgment on by the numerical value of shock strength, notched Izod impact strength, tensile strength, flexural strength and the modulus in flexure of test gained.Embodiment, Comparative Examples prescription and every The performance test results be Lie Gebiao as follows:
Table 1 embodiment 1-5 and Comparative Examples 1-2 material prescription table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | |
| Co-polypropylene, weight % | ??39.6 | ??44.6 | ??49.6 | ??49.6 | ??49.6 | ??44.6 | ??49.6 |
| The PP compatilizer, weight % | ??20 | ??15 | ??10 | ??10 | ??10 | ??15 | ??10 |
| Talcum powder, weight % | ??5 | ??10 | ??20 | ??25 | ??30 | ??40 | ??40 |
| The calcium salt whisker, weight % | ??35 | ??30 | ??20 | ??15 | ??10 | ??- | ??- |
| Antioxidant 3114, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
| Oxidation inhibitor DSTP, weight % | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Oxidation inhibitor 168, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
Test result of each prescription is referring to table 2:
Table 2 embodiment 1-5 and Comparative Examples 1-2 test result
| Sequence number | Test rating | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 |
| ??1 | Tensile strength, MPa | ??78.7 | ??73.4 | ??57.0 | ??48.1 | ??43.5 | ??39.5 | ??38.2 |
| ??2 | Flexural strength, MPa | ??99.1 | ??94.6 | ??73.9 | ??73.7 | ??73.5 | ??65.2 | ??63.5 |
| ??3 | Modulus in flexure, MPa | ??5021.4 | ??4927.7 | ??3733.7 | ??3554.9 | ??3494.4 | ??3028 | ??2880 |
| ??4 | Notched Izod impact strength, kJ/m^2 | ??11.8 | ??13.4 | ??15.8 | ??16.4 | ??17.9 | ??15.9 | ??18.5 |
From the contrast of embodiment 1-5 and Comparative Examples 1,2 as can be seen, compare with the talcum powder binary system with polypropylene, calcium salt whisker and talcous compound system have obvious help for the rigidity that improves matrix material, still can keep the toughness of matrix material simultaneously.Find out from the mutual contrast of embodiment 1-5 that simultaneously calcium salt whisker content is high more, then the rigidity of matrix material is high more, and toughness decreases.
Claims (10)
1. the composition of a mineral/whisker toughening-reinforcing polypropylene, formulated by following raw materials by weight percent:
Polypropylene 50-70
Whisker toughener 3-15
Other mineral fillers 15-35
PP compatilizer 3-10
Oxidation inhibitor 0.1-2
Other auxiliary agents 0-5.
2. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 1 is characterized in that: described polypropylene is different mobile homo-polypropylene and block copolymerization propylene; Melt flow rate (MFR) is 2～60g/10min.
3. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 2, it is characterized in that: the comonomer of described block copolymerization propylene is an ethene, and its content is in the scope of 4～10mol%.
4. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 2, it is characterized in that: the degree of crystallinity of described homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
5. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 1, it is characterized in that: described whisker toughener is the calcium salt whisker, its length-to-diameter ratio L/D＞40, particle diameter＜10 μ m.
6. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 1, it is characterized in that: described PP compatilizer is the oligopolymer of the graftomer of polypropylene and maleic anhydride, its melt flow rate (MFR) is 5-30g/10min, and the maleic anhydride graft amount is 0.5-2.5%.
7. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 1, it is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant is hindered phenol or thioesters kind antioxidant; Auxiliary anti-oxidant is the phosphorite kind antioxidant.
8. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 7 is characterized in that: described primary antioxidant be 3114,1010 and DSTP wherein one or more; Auxiliary anti-oxidant is 618 and 168.
9. the composition of a kind of mineral/whisker toughening-reinforcing polypropylene according to claim 1, it is characterized in that: described other mineral fillers are one or more mixtures in talcum powder, lime carbonate, mica and the barium sulfate, and its particle size range is 1～10 micron.
10. composition method for preparing the described mineral/whisker toughening-reinforcing polypropylene of claim 1, its concrete steps are:
(1) takes by weighing raw material by proportioning;
(2) with mineral surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(3) with calcium salt whisker surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue, titanate coupling agent homologue or aluminate coupling agent homologue;
(4) place high mixer together under 90-120 ℃ of condition polypropylene, other mineral fillers, PP grafting compatilizer, oxidation inhibitor and other auxiliary agent, mixed 3 minutes;
(5) raw materials mixed is placed dual-screw-stem machine,, the calcium salt whisker is joined in the forcing machine by the way of side direction feeding, extruding pelletization, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070842A (en) * | 2010-12-30 | 2011-05-25 | 金发科技股份有限公司 | High heat resistance low density high performance auto polypropylene composite and preparation method thereof |
| CN102388974A (en) * | 2011-11-14 | 2012-03-28 | 江苏星驰生物科技有限公司 | Bovine colostrums formula powder |
| CN102516662A (en) * | 2011-12-08 | 2012-06-27 | 上海普利特复合材料股份有限公司 | Polypropylene composite material with high strength and high heat resistance and its preparation method |
| CN103497425A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | High-strength and high-tenacity polypropylene composite materials and preparation method thereof |
| CN103665544A (en) * | 2013-11-20 | 2014-03-26 | 天津金发新材料有限公司 | Isotropic polypropylene composition with low linear expansion coefficient and preparation method thereof |
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| CN106700234A (en) * | 2015-11-15 | 2017-05-24 | 合肥杰事杰新材料股份有限公司 | Canasite glass ceramic reinforced polypropylene material and preparation method therefor |
| CN111592714A (en) * | 2020-04-20 | 2020-08-28 | 湖州正鸣塑胶科技有限公司 | Whisker reinforced composite PP material, preparation method thereof and plastic pipeline |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102070842B (en) * | 2010-12-30 | 2012-11-21 | 金发科技股份有限公司 | High heat resistance low density high performance auto polypropylene composite and preparation method thereof |
| CN102070842A (en) * | 2010-12-30 | 2011-05-25 | 金发科技股份有限公司 | High heat resistance low density high performance auto polypropylene composite and preparation method thereof |
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| CN102516662A (en) * | 2011-12-08 | 2012-06-27 | 上海普利特复合材料股份有限公司 | Polypropylene composite material with high strength and high heat resistance and its preparation method |
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Application publication date: 20100630 |